CN1689701A - 含10mr沸石和12mr沸石的催化剂及其在烷基芳族烃烷基转移中的应用 - Google Patents
含10mr沸石和12mr沸石的催化剂及其在烷基芳族烃烷基转移中的应用 Download PDFInfo
- Publication number
- CN1689701A CN1689701A CN200510065741.9A CN200510065741A CN1689701A CN 1689701 A CN1689701 A CN 1689701A CN 200510065741 A CN200510065741 A CN 200510065741A CN 1689701 A CN1689701 A CN 1689701A
- Authority
- CN
- China
- Prior art keywords
- zeolite
- catalyzer
- metal
- application
- arbitrary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 150
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 130
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 22
- 238000010555 transalkylation reaction Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 74
- 239000002184 metal Substances 0.000 claims abstract description 74
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- -1 VIB metals Chemical class 0.000 claims abstract description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 2
- 239000000203 mixture Substances 0.000 description 22
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical group CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
描述了一种催化剂,它含有至少一种具有通道的沸石,这种沸石通道开口是由有10个氧原子的环确定的(10MR);至少一种具有至少通道或侧袋的沸石,这种沸石通道或侧袋开口是由有12个氧原子的环确定的(12MR);至少一种选自第IIIA和VIIB族金属的金属和至少一种多孔的无机基体。所述的催化剂还任选地含有至少一种选自第IVA和VIB族金属的金属。本发明的催化剂用于烷基芳族烃的烷基转移方法,所述的烷基芳族烃例如是甲苯或苯和具有至少9个碳原子的烷基芳族化合物。
Description
技术领域
本发明涉及一种例如用于芳族烃转化反应的催化剂。更确切地,本发明涉及一种烷基芳族烃的烷基转移作用催化剂,优选地生产二甲苯所使用的苯或甲苯和具有至少9个碳原子的芳族化合物的烷基转移作用催化剂。本发明还涉及所述催化剂的制备方法及其在烷基芳族烃烷基转移方法中的应用。
背景技术
在现有技术中已经描述了许多歧化作用和/或烷基转移作用催化剂,这些催化剂是发光沸石基的(US-A-3 506 731、US-A-4 151 120、US-A-4 180 693、US-A-4 210 770、US-A-3 281 483、US-A-3 780 121或US-A-3 629 351),或ω沸石基的(US-A-5 210 356、US-A-5 371311)。
专利申请EP-A1-0 731 071描述了,在含有芳族化合物(其有至少一个乙基基团)的芳族C9馏分的烷基转移作用时,使用一种基于发光沸石和金属(Re、Ni、Co、Mo、Cr和W)的催化剂。
专利申请FR-A-2 744 650描述了以发光沸石结构类和针沸石结构类的沸石为主要成分的烷基芳族烃歧化作用/烷基转移作用复合催化剂的应用。
专利US 5 942 651描述了一种催化系统,该系统含有两种分开的和不连续的催化组合物,一种是以负载指数(indice de contrainte)0.5-3的沸石和贵金属为主要成分的,另一种是以负载指数3-12的沸石而无添加金属为主要成分的。专利US 5 905 051披露了一种催化系统,该系统含有用金属升级的以β沸石为主要成分的第一种催化组合物,和以其上浸渍助催化剂(S、P、Si)的ZSM-5沸石为主要成分的第二种催化组合物。这些文件公开的这些催化系统可用于每个分子有至少9个碳原子的芳族化合物的转化方法。
发明内容
本发明涉及一种催化剂,它含有至少一种有通道的沸石,这种沸石通道开口是由有10个氧原子的环确定的(10MR);至少一种有至少通道或侧袋的沸石,这种沸石通道或侧袋开口是由有12个氧原子的环确定的(12MR);至少一种选自第IIIA和VIIB族金属的金属和至少一种多孔的无机基体。本发明的催化剂还任选地含有至少一种选自第IVA和VIB族金属的金属。本发明催化剂中的每种沸石都含有硅和至少一种选自铝、铁、镓和硼的元素T。本发明的催化剂没有任何的第VIII族金属。
本发明还涉及所述的催化剂在烷基芳族烃烷基转移方法中的应用,所述的烷基芳族烃例如是甲苯和具有至少9个碳原子的烷基芳族化合物,或苯和具有至少9个碳原子的烷基芳族化合物。这种催化剂是处理C9+芳族物料的性能非常优良的催化剂,其物料含有一定百分数的具有至少10个碳原子的芳族化合物分子,并且远高于5重量%,这种物料还可以含有苯。
本发明的优点
已惊奇地发现一种复合催化剂,它含有至少一种有通道的沸石,这种沸石通道开口是由有10个氧原子的环确定的(10MR),和至少一种有至少一些通道或侧袋的沸石,这种沸石的通道或侧袋开口是由有12个氧原子的环确定的(12MR),以及至少一种选自第IIIA和VIIB族金属的金属的组合,所述的催化剂在烷基芳族烃,例如甲苯或苯歧化反应中和/或在烷基芳族烃,例如是甲苯、苯和三甲苯或具有9个以上碳原子的烷基芳族化合物(C9+)的烷基转移反应中的催化性能获得改善,特别是催化剂的活性、稳定性和选择性性能获得改善。本发明的催化剂对于处理含有高百分数(高于5重量%)的有10个和10个以上碳原子的芳族分子的芳族化合物原料C9+是非常有效的,这样能够使这些重分子在二甲苯中价值增长,所述的重分子例如是二甲基乙苯、二乙苯,它们一般有具有一个以上碳原子的烷基(乙基、丙基等)。在苯或甲苯和烷基芳族化合物的烷基转移方法中使用本发明的催化剂时,它得到苯和二甲苯(高附加值产品)的产率比使用现有技术中已知催化剂得到的产率会明显高些。
此外,调整本发明催化剂中两种沸石的相对量,即10MR的量和至少12MR的量时,有可能处理非常宽范围的含烃物料混合物。
本发明的描述
本发明的目的是一种催化剂,它含有至少一种有通道的沸石,这种沸石通道开口是由有10个氧原子的环确定的(10MR);至少一种有至少通道或侧袋的沸石,这种沸石通道或侧袋开口是由有12个氧原子的环确定的(12MR),至少一种选自第IIIA和VIIB族金属的金属和至少一种多孔无机基体。本发明的催化剂没有任何第VIII族金属。
在W.M.Meier,D.H.Olson和Ch.Baerlocher,第5次修定版,2001年,Elsevier“沸石结构类型图谱集”分类中定义了这些沸石,本申请也参考其分类法。其中,根据其孔或通道开口尺寸对这些沸石进行分类。按照本发明,本发明催化剂中含有的至少一种沸石具有孔或通道,它们的开口由具有10个氧原子的环(具有10MR的开口)确定,而本发明催化剂中含有的至少一种另外的沸石具有至少孔或通道或侧袋,它们的开口由具有12个氧原子的环(具有至少12MR的开口)确定。根据本发明,在本说明书下面用10MR沸石表示具有10MR开口的沸石,这种沸石的通道是直接通向所述沸石外部的主要通道。在本说明书下面用具有至少12MR的沸石表示具有至少12MR开口的沸石,这种沸石至少具有或者直接通向所述沸石外部的主要通道12MR,或者仅仅通过具有除12MR之外开口的主要通道到达的次级通道12MR,或者其开口由具有12个氧原子的环确定的侧袋。本发明催化剂中的这些10MR和至少12MR沸石含有硅和至少一种元素T,它选自铝、铁、镓和硼,优选地铝。这些催化剂优选地几乎完全呈酸形式。
本发明催化剂中这种10MR沸石的特征在于Si/Al比是2-250,优选地5-150,非常优选地10-80。以干燥沸石总重量计,钠含量小于0.2重量%,优选地小于0.1重量%,非常优选地小于0.05重量%。在现有技术中已知的,具有其开口由有10个氧原子的环确定的(10MR)通道的所有这些沸石都适合于加工成本发明的催化剂。这些优选的10MR沸石选自ZSM-5、IM-5和ZSM-22沸石。本技术领域的技术人员都熟知这些沸石及其制备方法。
本发明催化剂中这种至少12MR沸石的特征在于Si/Al比是2-250,优选地5-150,非常优选地10-80。以干燥沸石总重量计,钠含量小于0.2重量%,优选地小于0.1重量%,非常优选地小于0.05重量%。在现有技术中已知的,具有其开口由有12个氧原子的环确定的(12MR)通道(主要的或次级的)或侧袋的所有这些沸石都适合于加工成本发明的催化剂。在本发明内优选的这些至少12MR沸石选自β、Y、发光沸石、NU-87、ITQ-23、EU-1和boggsite沸石。NES结构类的NU-87沸石具有10MR主要通道,还具有通过这些10MR通道可到达的12MR次级通道,例如在M.L.Occelli和H.E.Robson编辑的“微孔材料合成(Synthesis of microporous materials)”第1卷,第24章(CasciJ.L等人)中所描述的。boggsite沸石具有10MR和12MR主要通道。EU-1沸石具有10MR主要通道和12MR侧袋。本技术领域的技术人员都熟知这些沸石及其制备方法。
上述沸石的Si/Al比是所述沸石合成后达到的比,或是本技术领域的技术人员都熟知的在后合成脱铝作用处理后达到的比,其非穷举实例是水热处理,接着或不接着酸侵蚀或用无机酸或有机酸溶液直接酸侵蚀。
本发明催化剂中10MR和至少12MR沸石的总Si/Al比以及这些试样的化学组成都是采用X荧光分析和原子吸收法测定的。
本发明催化剂组合物中的这些10MR和至少12MR沸石可以进行煅烧,并且用至少一种铵盐溶液通过至少一次处理可以进行交换,得到沸石的铵盐形式,这种形式一旦煅烧就能得到所述沸石的氢形式。
本发明催化剂组合物中的这些10MR和至少12MR沸石至少部分地,优选地几乎全部地呈酸形式,即呈氢形式(H+)。Na/T原子比一般小于10%,优选地小于5%,更优选地小于1%。
所述的催化剂还含有至少一种选自第IIIA和VIIB族金属的金属,优选地其含量是以催化剂总重量计0.01-5重量%。在这些第VIIB族金属中,铼是优选的。在这些第IIIA族金属中,镓是优选的。本发明的催化剂任选地还含有至少一种选自第IVA和VIB族金属的金属,优选地其含量是以催化剂总重量计0.01-5重量%,更优选地0.5-3重量%。在这些第IVA族金属中,锡是优选的。在这些第VIB族金属中,钼是优选的。本发明的催化剂没有任何的第VIII族金属。
这种多孔无机基体的含量是以催化剂总重量计5-95%,优选地10-90%,更优选地15-85%,还更优选地20-80%,这种多孔无机基体一般选自粘土(例如选自如高岭土或膨润土的天然粘土)、氧化镁、氧化铝、二氧化硅、氧化钛、氧化硼、二氧化锆、磷酸铝、磷酸钛、磷酸锆、二氧化硅-氧化铝和炭的这些元素,优选地选自氧化铝和粘土的这些元素,更优选地选自氧化铝。
这些10MR和至少12MR沸石已编入沸石图谱集中,并且根据这个著作(W.M.Meier,D.H.Olson和Ch.Baerlocher,第5修定版,2001年,“沸石结构类型图谱集”)所列参考文献描述的这些方法,或采用为本技术领域的技术人员公开的参考文献描述的任何其它方法可以合成出这些沸石。另外,还可以使用任何商品沸石以得到本发明的催化剂。
根据第一个制备本发明催化剂的实施方案,在催化剂成型之前,让本发明催化剂含有的前面已描述的至少一种沸石沉积至少一种选自第IIIA和VIIB族金属的金属。优选地,让至少一种10MR沸石沉积至少一种选自第IIIA和VIIB族金属的金属。还可能的是让这种10MR沸石沉积选自第IIIA和VIIB族金属的金属,让这种至少12MR沸石沉积选自第IIIA和VIIB族金属的另一种金属。有利地,本发明的催化剂含有至少一种选自第IIIA和VIIB族金属的金属和至少一种选自第IVA和VIB族金属的金属时,让这种10MR沸石沉积选自第IIIA和VIIB族金属的金属,而让这种至少12MR沸石沉积选自第IVA和VIB族金属的金属。将如此负载这些金属的这些沸石混合起来。可以采用本技术领域的技术人员已知的任何粉末混合技术,将这时呈粉末状的这些沸石混合起来。
负载金属的沸石粉末一旦混合,就马上采用本技术领域的技术人员已知的任何技术将这种粉末混合物成型。特别可以让其与一般为无定形的多孔无机基体混合,例如与湿的氧化铝凝胶粉末混合。这种混合物然后例如通过模具挤塑成型。
可以使用除氧化铝之外的其它基体进行成型,其它的基体例如像氧化镁、无定形二氧化硅-氧化铝、天然粘土(高岭土、膨润土、海泡石、绿坡缕石)、二氧化硅、氧化钛、氧化硼、二氧化锆、磷酸铝、磷酸钛、磷酸锆、炭及其混合物。优选使用呈本技术领域的技术人员已知任何形式的含有氧化铝的基体,更优选地氧化铝,例如γ氧化铝。使用氧化铝与二氧化硅的混合物、氧化铝与二氧化硅-氧化铝混合物也可是很有利。可以采用除挤塑外的其它技术,例如制片或催化剂滚球形成。
在成形步骤后,得到的产物进行干燥步骤,再进行煅烧步骤。
根据第二个制备本发明催化剂的实施方案,可以采用本技术领域的技术人员已知的并能够将金属沉积在沸石上的任何方法,在无金属的沸石成型后,将至少一种选自第IIIA和VIIB族金属的金属和任选地至少一种选自第IVA和VIB族金属的金属沉积在其载体上。术语“载体”意指在成型、干燥与煅烧之后,沸石(无金属)与至少一种无机多孔基体的混合物。
本发明的催化剂载体一般有其下述基体和沸石含量:
-5-95重量%,优选地10-90重量%,更优选地15-85重量%,非常优选地20-80重量%沸石,使得至少一种沸石选自10MR沸石和至少一种沸石选自至少12MR沸石,
-5-95重量%,优选地10-90重量%,更优选地15-85重量%,非常优选地20-80重量%至少一种无定形或结晶不好的氧化物类多孔无机基体。
为了根据本发明第一个和第二个催化剂制备方法将金属沉积在这些沸石上,可以采用有竞争的阳离子交换技术,其中竞争者优选地是硝酸铵,竞争比是至少等于约20,有利地约30-200。还可以采用干浸渍技术或共沉淀技术。
可以使用的第VIIB族金属源也是本技术领域的技术人员熟知的。在铼的情况下,通常使用高铼酸铵配合物(NH4)ReO4或高铼酸。可以使用的第IIIA族金属源也是本技术领域的技术人员熟知的。在镓的情况下,硝酸镓Ga(NO3)3是优选的。可以使用的第VIB族金属源也是本技术领域的技术人员熟知的。在钼的情况下,可以使用钼酸及其盐,特别地铵盐,例如钼酸铵、七钼酸铵,以及磷钼酸。优选地,使用七钼酸铵(NH4)6Mo7O24。在一种或多种第IIIA和VIIB族和任选地第IVA和VIB族金属沉积后,一般在空气或氧气下进行煅烧,通常在300-600℃下煅烧0.5-10小时,优选地在350-550℃下煅烧1-4小时。然后在氢气下进行还原反应,一般在300-600℃下还原1-10小时,优选地在350-550℃下还原2-5小时。
也可以将金属不直接沉积在这些沸石上,而是还可以在成形步骤前后将金属直接沉积在载体的多孔无机基体(例如铝粘合剂)上,同时进行阴离子交换。在沉积铼的情况下,对铼例如可以列举使用高铼酸HReO4。一般而言,如前面所述,在沉积金属后,这种催化剂如前面所指出地进行煅烧,然后在氢气下进行还原。
在本发明的其它实施方案中,每种沸石使用粘合剂独立成型。可以在成型(挤出物或颗粒)后混合这些沸石。在成型沸石混合前或后,优选地在成型沸石混合前沉积这些金属。因此,可以将不同的金属沉积这两种成形的沸石上。优选地,钼沉积在两种沸石中的一种沸石上,优选地沉积在至少12MR沸石上。
在含有多种金属的催化剂情况下,可以或者以同样方式,或者根据采用的催化剂制备实施方案,以任何顺序,在成形前或后采用不同的技术加入这些金属。在采用的技术是离子交换技术的情况下,为了加入要求量的金属,可需要进行多次相继的交换。
不管本发明催化剂制备实施方案如何,都可以在煅烧所述催化剂后在氢气下,通常在温度300-600℃,优选地350-550℃下还原1-10小时,优选地2-5小时。可以在相对于一定反应中所述催化剂使用地的原地或非原地进行这样一种还原反应。
在前面定义的每组沸石中,两种沸石之间的分配是使得选自10MR沸石中的一种或多种沸石含量可以是以加入这种催化剂中总沸石相对百分数计1-99%,优选地5-95%,更优选地10-99%。同样,至少12MR沸石含量是以加入这种催化剂中总沸石相对百分数计1-99%,优选地5-95%,更优选地10-99%。
本发明的催化剂可以制成具有不同形状和尺寸的颗粒。这种催化剂通常使用圆柱或多波瓣挤塑物,例如直的或扭转形的双波瓣、三波瓣挤塑物、多波瓣挤塑物,但任选地可以生产与使用研碎的粉末、片、环、珠、轮状物。非常优选地,本发明的催化剂含有至少一种选自在10MR沸石上的第IIIA和VIIB族金属的金属。
本发明的催化剂任选地可以含有硫。在这种情况下,这种硫或者在催化反应之前就地,或者非就地加到煅烧的成型催化剂中,该催化剂含有一种或多种前面列举的元素。使用本技术领域的技术人员熟知的任何硫化剂,例如像二甲基二硫醚或硫化氢,进行这种硫化反应。这种任选的硫化反应可在还原反应后进行。在原地硫化的情况下,如果该催化剂没有预先被还原,则在硫化反应前进行这种还原反应。在非原地硫化的情况下,先进行这个还原反应,然后进行这个硫化反应。
本发明的催化剂用于转化烃。
本发明特别涉及所述催化剂在烷基芳族烃物料烷基转移方法中的应用,优选地使用苯-AC9 +或甲苯-AC9 +混合物(其中AC9 +表示每个分子含有至少9个碳原子的烷基芳族烃),使苯或甲苯和烷基芳族化合物一般地烷基转移成C9 +的应用,其中该混合物含有以总混合物计1-100%AC9 +。所述的催化剂对于所述的应用显得非常有效,因为这种催化剂显示出特别的活性、选择性和稳定性,甚至在含有大量重芳族化合物AC9 +的待处理物料存在下也如此,这些重芳族化合物可以含有高比例的AC10 +。含有至少5重量%,直到25重量%,甚至更高的AC10 +的物料AC9 +都可得到增值。作为实例,非穷举列出二甲基乙苯、二乙苯、丙基乙苯等。因此,在重烷基芳族化合物烷基转移反应中使用这种催化剂是特别有意义的。
所述应用的操作条件通常如下:温度是250-650℃,优选地350-550℃;压力是1-6MPa,优选地2-4.5MPa;加料空间速度(以每千克催化剂每小时加入物料千克数表示)是0.1-10h-1,优选地0.5-4h-1;氢与烃的摩尔比是2-20摩尔/摩尔,优选地3-12摩尔/摩尔。
具体实施方式
下面这些实施例说明本发明而不限制其保护范围。
实施例1:制备10MR沸石基催化剂(对比),制备至少12MR沸石基催化剂(对比),以及制备10MR沸石和至少12MR沸石基催化剂(根据本发明)。
在表1中列出了为制备举例说明本发明的这些催化剂而使用的沸石,还列出它们的组成(Si/Al原子比)与它们的钠残留含量。相关五种沸石都是呈酸形式的。
β沸石、发光沸石和ZSM-5沸石都是商品沸石(PQ)。
NU-87沸石是根据欧洲专利申请EP-A-0 377 291或专利EP-B-0378 916制备的。这种沸石的总Si/Al原子比等于17.2,钠的重量含量等于1256ppm。这种NU-87沸石首先在空气和氮气流下在550℃进行所谓干燥煅烧6小时。然后,得到的固体在10N NH4NO3溶液中在约100℃进行离子交换4小时。这种NU-87沸石这时在约100℃下用7N硝酸溶液处理5小时。加入的硝酸溶液体积(以ml表示)是干燥NU-87沸石重量P的10倍(V/P=10)。在同样的操作条件下使用7N硝酸溶液重复处理两次。
这些处理后,得到的沸石为H形式,其总Si/Al原子比等于33.3,Na含量10ppm。
根据专利申请FR-A-2 754 809或专利US 6 136 290的实施例1合成了IM-5沸石。
表1:10MR沸石与至少12MR沸石
沸石 | Si/Al(FX) | Na(ppm) | 类型 |
β | 12.5 | 87 | 12MR |
ZSM-5 | 17.5 | 132 | 10MR |
MOR | 10 | 109 | 12MR |
IM-5 | 12 | 84 | 10MR |
NU-87 | 33.3 | 10 | 10&12MR |
使用氧化铝凝胶,采用挤塑法使这些沸石成型,以便在干燥空气下干燥与煅烧后得到一种载体,它含有以重量计80%沸石和20%氧化铝。该载体的沸石部分由单一沸石(非本发明)组成,或由成型前混合的两种不同沸石机械混合物组成(本发明)。
为了制备催化剂A-N,含有一种沸石和两种不同沸石混合物的沸石载体将使用的金属前体溶液(铼为高铼酸铵,钼为七钼酸铵,镓为硝酸镓,镍为硝酸镍)浸渍至干,以便沉积达到所要求的金属百分数。这种湿固体再在120℃下干燥12小时,然后在干燥空气流下在温度500℃煅烧1小时。所得到催化剂的组成列于表2。
对于催化剂O和P,含有沉积钼(催化剂M)或镓(催化剂N)的β沸石的挤塑载体,分别与含有沉积铼(催化剂B)的ZSM-5沸石的挤塑载体进行机械混合。
表2:含有10MR沸石(非本发明),至少12MR沸石(非本发明),以及10MR沸石和至少12MR沸石(根据本发明)的催化剂
催化剂 | %Al2O3 | 一种或多种沸石 | 沸石比 | %金属 |
A | 20 | β | 100 | 0.5%Re |
B | 20 | ZSM-5 | 100 | 0.5%Re |
C | 20 | MOR | 100 | 0.5%Re |
D | 20 | IM-5 | 100 | 0.25%Re |
E | 20 | NU-87 | 100 | 0.25%Re |
F | 20 | β+ZSM-5 | 50/50 | 0.5%Re |
G | 20 | MOR+ZSM-5 | 50/50 | 0.5%Re |
H | 20 | NU-87+ZSM-5 | 50/50 | 0.25%Re |
I | 20 | β+IM-5 | 50/50 | 0.25%Re |
J | 20 | NU-87+IM-5 | 34/66 | 0.25%Re |
K | 20 | NU-87+IM-5 | 66/34 | 0.25%Re |
M | 20 | β | 100 | 1%Mo |
N | 20 | β | 100 | 1%Ga |
O | 20 | β+ZSM-5 | 50/50 | 0.5%Mo/β0.25%Re/ZSM-5 |
P | 20 | β+ZSM-5 | 50/50 | 0.5%Ga/β0.25%Re/ZSM-5 |
实施例2:10MR沸石基催化剂(对比),至少12MR沸石基催化剂(对比),以及10MR沸石和至少12MR沸石基催化剂(根据本发明)的催化性能
这些催化剂在氢气下在450℃预先还原2小时。
在下述操作条件下进行了这些催化试验:
-温度:400℃
-压力:25巴
-H2/HC=8.5摩尔/摩尔
-WHSV=4h-1(每克催化剂每小时的物料质量)。
这种物料由50%甲苯、16%乙基甲苯、28%三甲苯和6%具有至少10个碳原子的芳族化合物组成。
催化剂 | A | B | C | D | E |
总转化率(%) | 58.9 | 40.1 | 56.9 | 45.8 | 50.3 |
产率(%重量) | |||||
轻烃(C1-C4) | 16.1 | 9.5 | 9.5 | 4.6 | 4.6 |
苯+二甲苯 | 33.6 | 23.8 | 38.1 | 33.1 | 37.8 |
乙基苯 | 1.6 | 0.1 | 0.7 | 0.5 | 1.0 |
重烃 | 5.6 | 2 | 3.1 | 4.3 | 4.3 |
催化剂 | F | G | H | I | J | K |
总转化率(%) | 56.0 | 51.9 | 52.3 | 51.1 | 50.9 | 52.0 |
产率(%重量) | ||||||
轻烃(C1-C4) | 7.5 | 6.6 | 5.6 | 7.3 | 5.1 | 4.6 |
苯+二甲苯 | 41.4 | 39.4 | 39.2 | 37.0 | 38.7 | 39.5 |
乙苯 | 0.1 | 0.2 | 0.2 | 0.5 | 0.4 | 0.5 |
重烃 | 2.5 | 2.5 | 3.2 | 2.7 | 3.2 | 3.7 |
催化剂 | M | N | O | P |
总转化率(%) | 57.6 | 56.2 | 57.3 | 57.1 |
产率(%重量) | ||||
轻烃(C1-C4) | 13.3 | 14.1 | 8.2 | 7.8 |
苯+二甲苯 | 34.5 | 34.8 | 41.8 | 40.9 |
乙苯 | 1.3 | 1.2 | 0.3 | 0.2 |
重烃 | 6.1 | 7.3 | 3.6 | 4.3 |
在本发明中含有由至少一种10MR沸石和至少一种至少12MR沸石组成的混合物的催化剂的应用能够提高二甲苯和苯的产率,这些是烷基转移反应的目标产物,因为它们是高增值的。
Claims (12)
1.催化剂,它含有至少一种有通道的沸石,这种沸石通道开口是由有10个氧原子的环确定的(10MR);至少一种有至少通道或侧袋的沸石,这种沸石通道或侧袋开口是由有12个氧原子的环确定的(12MR),至少一种选自第IIIA和VIIB族金属的金属,至少一种多孔无机基体,所述的催化剂没有任何第VIII族金属。
2.根据权利要求1所述的催化剂,其中这种沸石具有通道,其开口是由有10个氧原子的环确定的,该沸石选自ZSM-5、IM-5和ZSM-22沸石。
3.根据权利要求1或2所述的催化剂,其中这种沸石具有至少通道或侧袋,其通道或侧袋开口是由有12个氧原子的环确定的,该沸石选自β、Y、发光沸石、NU-87、EU-1和boggsite沸石。
4.根据权利要求1-3中任一权利要求所述的催化剂,它含有至少一种选自第IVA和VIB族金属的金属。
5.根据权利要求1-4中任一权利要求所述的催化剂,其中第VIIB族金属是铼。
6.根据权利要求1-5中任一权利要求所述的催化剂,其中第IIIA族金属是镓。
7.根据权利要求1-6中任一权利要求所述的催化剂,其中第VIB族金属是钼。
8.根据权利要求1-7中任一权利要求所述的催化剂,它含有硫。
9.根据权利要求1-8中任一权利要求所述的催化剂在烷基芳族烃物料烷基转移方法中的应用。
10.根据权利要求9所述的应用,该应用是在苯或甲苯和每个分子有至少9个碳原子的烷基芳族烃的烷基转移方法中的应用。
11.根据权利要求10所述的应用,该应用是在处理含有至少5重量%有至少10个碳原子的芳族化合物的芳族化合物物料中的应用。
12.根据权利要求9-11中任一权利要求所述的应用,该应用是在下述条件下的应用:温度是250-650℃;压力是1-6MPa;以每千克催化剂每小时加入物料千克数表示的加料空间速度是0.1-10h-1;氢与烃的摩尔比是2-20。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0403887 | 2004-04-14 | ||
FR04/03887 | 2004-04-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1689701A true CN1689701A (zh) | 2005-11-02 |
CN1689701B CN1689701B (zh) | 2011-07-27 |
Family
ID=34942028
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200510065741.9A Expired - Fee Related CN1689701B (zh) | 2004-04-14 | 2005-04-14 | 含10mr沸石和12mr沸石的催化剂及其在烷基芳族烃烷基转移中的应用 |
Country Status (9)
Country | Link |
---|---|
US (1) | US7419931B2 (zh) |
EP (1) | EP1586376B1 (zh) |
JP (1) | JP2005296950A (zh) |
CN (1) | CN1689701B (zh) |
AT (1) | ATE435068T1 (zh) |
DE (1) | DE602005015154D1 (zh) |
DK (1) | DK1586376T3 (zh) |
ES (1) | ES2327753T3 (zh) |
ZA (1) | ZA200502559B (zh) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101842336A (zh) * | 2007-10-31 | 2010-09-22 | 埃克森美孚化学专利公司 | 重芳烃加工催化剂及其使用方法 |
CN102066529A (zh) * | 2008-06-26 | 2011-05-18 | 环球油品公司 | 新型烷基转移方法 |
CN104870407A (zh) * | 2012-12-12 | 2015-08-26 | 环球油品公司 | 使用uzm-44铝硅酸盐沸石的芳香族烷基转移方法 |
CN106976889A (zh) * | 2017-06-02 | 2017-07-25 | 中山大学 | 具有bog结构的硅铝沸石分子筛及其制备方法 |
CN108246354A (zh) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | 一种催化剂、其制备方法及二甲苯的制备方法 |
CN113164936A (zh) * | 2018-03-14 | 2021-07-23 | 沙特阿拉伯石油公司 | 通过金属浸渍的ZSM-5+纳米晶体β沸石复合催化剂;所述复合催化剂将重质重整产物转化为BTX的方法 |
Families Citing this family (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2861320B1 (fr) * | 2003-10-24 | 2005-12-30 | Inst Francais Du Petrole | Catalyseur comprenant au moins une zeolithe de type structural bog et son utilisation en transalkylation d'hydrocarbures alkylaromatiques |
FR2895283B1 (fr) | 2005-12-22 | 2008-02-01 | Inst Francais Du Petrole | Catalyseur comprenant une zeolithe euo, une zeolithe 10mr et une zeolithe 12mr et son utilisation en isomerisation des composes c8 aromatiques |
FR2895282B1 (fr) * | 2005-12-22 | 2008-02-01 | Inst Francais Du Petrole | Catallyseur bizeolithique comprenant un metal du groupe viii et un metal du groupe iiia et son utilisation en isomerisation des composes c8 aromatiques |
EP1993979A4 (en) * | 2006-02-03 | 2011-07-06 | Grt Inc | CONTINUOUS PROCESS FOR CONVERTING NATURAL GAS TO LIQUID HYDROCARBONS |
EP1882728A3 (en) * | 2006-07-28 | 2008-05-14 | Uop Llc | Synergistic rhenium and germanium-containing catalysts potentiated with tin and alkylaromatic transalkylation processes using such catalysts |
US7456124B2 (en) | 2006-09-12 | 2008-11-25 | Uop Llc | Rhenium-containing transalkylation catalysts and processes for making the same |
EP2027918A1 (en) * | 2007-07-31 | 2009-02-25 | Total Petrochemicals Research Feluy | Mixtures of molecular sieves comprising MeAPO, their use in conversion of organics to olefins |
US8653315B2 (en) | 2008-07-30 | 2014-02-18 | King Fahd University Of Petroleum And Minerals | Multiple zeolite catalyst and method of using the same for toluene disproportionation |
US20100029467A1 (en) * | 2008-07-30 | 2010-02-04 | Tomoyuki Inui | Multiple zeolite catalyst |
CN201340888Y (zh) * | 2009-01-08 | 2009-11-04 | 东莞新能源科技有限公司 | 锂离子电池 |
EP2527036A4 (en) * | 2010-01-20 | 2014-03-05 | Jx Nippon Oil & Energy Corp | CATALYST FOR USE IN THE PRODUCTION OF MONOCYCLIC AROMATIC HYDROCARBONS AND METHOD FOR THE PRODUCTION OF MONOCYCLIC AROMATIC HYDROCARBONS |
US8183424B2 (en) | 2010-02-03 | 2012-05-22 | Exxonmobil Chemical Patents Inc. | Transalkylation of heavy aromatic hydrocarbon feedstocks |
US8435909B2 (en) * | 2010-02-18 | 2013-05-07 | King Fahd University Of Petroleum And Minerals | Dual-zeolite catalyst for production of ethylbenzene |
WO2013096069A2 (en) | 2011-12-22 | 2013-06-27 | Uop Llc | Uzm-39 aluminosilicate zeolite |
JP5852749B2 (ja) | 2011-12-22 | 2016-02-03 | ユーオーピー エルエルシー | Uzm−39アルミノシリケートゼオライトを用いた芳香族化合物の転化反応 |
EP2874944A4 (en) | 2011-12-22 | 2016-04-27 | Uop Llc | HISTORICAL CONVERSION SYNTHESIS OF ZEOLITHES |
EP2834004B1 (en) | 2012-04-02 | 2020-12-23 | Saudi Arabian Oil Company | Multimetal zeolites based catalyst for transalkylation of heavy reformate to produce xylenes and petrochemical feedstocks |
US8912378B2 (en) | 2012-12-12 | 2014-12-16 | Uop Llc | Dehydrocyclodimerization using UZM-39 aluminosilicate zeolite |
US8609910B1 (en) | 2012-12-12 | 2013-12-17 | Uop Llc | Catalytic pyrolysis using UZM-39 aluminosilicate zeolite |
US8889939B2 (en) | 2012-12-12 | 2014-11-18 | Uop Llc | Dehydrocyclodimerization using UZM-44 aluminosilicate zeolite |
US8618343B1 (en) | 2012-12-12 | 2013-12-31 | Uop Llc | Aromatic transalkylation using UZM-39 aluminosilicate zeolite |
US8609920B1 (en) | 2012-12-12 | 2013-12-17 | Uop Llc | UZM-44 aluminosilicate zeolite |
US8609911B1 (en) | 2012-12-12 | 2013-12-17 | Uop Llc | Catalytic pyrolysis using UZM-44 aluminosilicate zeolite |
US8609919B1 (en) | 2012-12-12 | 2013-12-17 | Uop Llc | Aromatic transformation using UZM-44 aluminosilicate zeolite |
US8921634B2 (en) | 2012-12-12 | 2014-12-30 | Uop Llc | Conversion of methane to aromatic compounds using UZM-44 aluminosilicate zeolite |
WO2014093461A1 (en) | 2012-12-12 | 2014-06-19 | Uop Llc | Conversion of methane to aromatic compounds using uzm-39 aluminosilicate zeolite |
AU2013369466A1 (en) * | 2012-12-31 | 2015-04-16 | Shell Internationale Research Maatschappij B.V. | Catalyst and method for preparation thereof |
CN105008492A (zh) | 2013-02-21 | 2015-10-28 | 吉坤日矿日石能源株式会社 | 单环芳香族烃的制造方法 |
FR3006608B1 (fr) * | 2013-06-10 | 2021-01-01 | Ifp Energies Now | Adsorbant a base d'une zeolithe et d'une argile riche en silice et procede de purification de charges d'hydrocarbures contenant des molecules insaturees |
JP6254882B2 (ja) * | 2014-03-26 | 2017-12-27 | コスモ石油株式会社 | キシレンの製造方法 |
US10053403B2 (en) | 2015-02-04 | 2018-08-21 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and their use in transalkylation of heavy aromatics to xylenes |
SG10202010226SA (en) | 2015-02-04 | 2020-11-27 | Exxonmobil Chemical Patents Inc | Process for preparing a molecular sieve |
US10118165B2 (en) | 2015-02-04 | 2018-11-06 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and use in heavy aromatics conversion processes |
PT3484619T (pt) * | 2016-07-13 | 2020-07-20 | Shell Int Research | Composição de catalisador compreendendo zeólito de tipo con e zeólito de tipo zsm-5, preparação e processo que utiliza tal composição |
US11097262B2 (en) * | 2017-06-15 | 2021-08-24 | Saudi Arabian Oil Company | Composite hierarchical zeolite catalyst for heavy reformate conversion to xylenes |
US10661260B2 (en) | 2017-06-15 | 2020-05-26 | King Fahd University Of Petroleum And Minerals | Zeolite composite catalysts for conversion of heavy reformate to xylenes |
EP3834931A1 (en) | 2018-03-14 | 2021-06-16 | Saudi Arabian Oil Company | Composite zeolite catalysts for heavy reformate conversion into xylenes |
EP3539652A1 (en) | 2018-03-14 | 2019-09-18 | Saudi Arabian Oil Company | Method of heavy reformate conversion into btx over metal-impregnated zsm-5+mesoporous mordenite zeolite composite catalyst |
EP3539651A1 (en) | 2018-03-14 | 2019-09-18 | Saudi Arabian Oil Company | Method of heavy reformate conversion into btx over metal-impregnated zsm-5+layered mordenite zeolite composite catalyst; said composite catalyst |
EP3539649B1 (en) * | 2018-03-14 | 2020-11-18 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
KR20210052665A (ko) | 2019-10-30 | 2021-05-11 | 에스케이이노베이션 주식회사 | 저감된 에틸벤젠 함량을 갖는 c8 방향족 탄화수소 제조용 촉매 및 이의 제조방법 |
US10981160B1 (en) | 2019-12-19 | 2021-04-20 | Saudi Arabian Oil Company | Composite hierarchical zeolite catalyst for heavy reformate conversion to xylenes |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5055176A (en) | 1988-12-30 | 1991-10-08 | Mobil Oil Corporation | Multi component catalyst and a process for catalytic cracking of heavy hydrocarbon feed to lighter products |
US5800698A (en) | 1994-12-30 | 1998-09-01 | Intevep, S.A. | Catalyst for the hydroisomerization of contaminated hydrocarbon feedstock |
US5759950A (en) | 1995-06-10 | 1998-06-02 | China Petrochemical Corporation | Catalyst supported with noble metal(s) for the isomerization of alkylaromatics |
US5905051A (en) * | 1997-06-04 | 1999-05-18 | Wu; An-Hsiang | Hydrotreating catalyst composition and processes therefor and therewith |
ES2259844T3 (es) * | 1998-12-24 | 2006-10-16 | Sk Corporation | Catalizador para la desproporcionacion/transalquilacion de hidrocarburos aromaticos y metodo para preparar el mismo. |
FR2790001B1 (fr) * | 1999-02-24 | 2001-04-27 | Inst Francais Du Petrole | Procede d'hydrocraquage avec un catalyseur comprenant une zeolithe im-5 et catalyseur comprenant une zeolithe im-5 et un element promoteur |
NL1014299C2 (nl) | 1999-02-24 | 2001-03-26 | Inst Francais Du Petrole | Werkwijze voor hydrokraken met een katalysator, die een zeoliet IM-5 bevat en katalysator, die een zeoliet IM-5 en een promotor-element bevat. |
FR2797593B1 (fr) * | 1999-08-19 | 2002-05-24 | Inst Francais Du Petrole | Catalyseur comprenant au moins une zeolithe de type structural nes et du rhenium et son utilisation en transalkylation d'hydrocarbures alkylaromatiques |
WO2003099719A1 (es) * | 2002-05-23 | 2003-12-04 | Consejo Superior De Investigaciones Cientificas | Material cristalino microporoso de naturaleza zeolítica (zeolita itq-22) su método de síntesis y su uso como catalizador |
US7148391B1 (en) | 2002-11-14 | 2006-12-12 | Exxonmobil Chemical Patents Inc. | Heavy aromatics processing |
-
2005
- 2005-03-22 ES ES05290631T patent/ES2327753T3/es active Active
- 2005-03-22 EP EP05290631A patent/EP1586376B1/fr not_active Not-in-force
- 2005-03-22 DK DK05290631T patent/DK1586376T3/da active
- 2005-03-22 AT AT05290631T patent/ATE435068T1/de not_active IP Right Cessation
- 2005-03-22 DE DE602005015154T patent/DE602005015154D1/de active Active
- 2005-03-30 ZA ZA200502559A patent/ZA200502559B/en unknown
- 2005-04-13 US US11/104,622 patent/US7419931B2/en not_active Expired - Fee Related
- 2005-04-14 CN CN200510065741.9A patent/CN1689701B/zh not_active Expired - Fee Related
- 2005-04-14 JP JP2005116360A patent/JP2005296950A/ja active Pending
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101842336A (zh) * | 2007-10-31 | 2010-09-22 | 埃克森美孚化学专利公司 | 重芳烃加工催化剂及其使用方法 |
CN101842336B (zh) * | 2007-10-31 | 2014-05-07 | 埃克森美孚化学专利公司 | 重芳烃加工催化剂及其使用方法 |
CN103934018B (zh) * | 2007-10-31 | 2016-08-17 | 埃克森美孚化学专利公司 | 重芳烃加工催化剂及其使用方法 |
CN102066529A (zh) * | 2008-06-26 | 2011-05-18 | 环球油品公司 | 新型烷基转移方法 |
CN102066529B (zh) * | 2008-06-26 | 2014-02-26 | 环球油品公司 | 烷基转移方法 |
CN104870407A (zh) * | 2012-12-12 | 2015-08-26 | 环球油品公司 | 使用uzm-44铝硅酸盐沸石的芳香族烷基转移方法 |
CN104870407B (zh) * | 2012-12-12 | 2017-04-05 | 环球油品公司 | 使用uzm‑44铝硅酸盐沸石的芳香族烷基转移方法 |
CN108246354A (zh) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | 一种催化剂、其制备方法及二甲苯的制备方法 |
CN108246354B (zh) * | 2016-12-28 | 2021-08-31 | 中国石油天然气股份有限公司 | 一种催化剂、其制备方法及二甲苯的制备方法 |
CN106976889A (zh) * | 2017-06-02 | 2017-07-25 | 中山大学 | 具有bog结构的硅铝沸石分子筛及其制备方法 |
CN106976889B (zh) * | 2017-06-02 | 2019-02-15 | 中山大学 | 具有bog结构的硅铝沸石分子筛及其制备方法 |
CN113164936A (zh) * | 2018-03-14 | 2021-07-23 | 沙特阿拉伯石油公司 | 通过金属浸渍的ZSM-5+纳米晶体β沸石复合催化剂;所述复合催化剂将重质重整产物转化为BTX的方法 |
Also Published As
Publication number | Publication date |
---|---|
DE602005015154D1 (de) | 2009-08-13 |
US20050234279A1 (en) | 2005-10-20 |
ZA200502559B (en) | 2006-07-26 |
DK1586376T3 (da) | 2009-10-12 |
ATE435068T1 (de) | 2009-07-15 |
EP1586376A1 (fr) | 2005-10-19 |
ES2327753T3 (es) | 2009-11-03 |
CN1689701B (zh) | 2011-07-27 |
US7419931B2 (en) | 2008-09-02 |
EP1586376B1 (fr) | 2009-07-01 |
JP2005296950A (ja) | 2005-10-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1689701A (zh) | 含10mr沸石和12mr沸石的催化剂及其在烷基芳族烃烷基转移中的应用 | |
CN101340977B (zh) | 包含euo沸石、10mr沸石和12mr沸石的催化剂及其在芳香族c8化合物的异构化中的应用 | |
US7629499B2 (en) | Process for transalkylation of alkyl-aromatic hydrocarbons used in two reaction zones | |
CN101340976B (zh) | 包含viii族金属和iiia族金属的双沸石催化剂及其在芳香族c8化合物的异构化中的应用 | |
CN1080248C (zh) | 重芳香族化合物的处理 | |
CN1934058A (zh) | 多环芳烃催化转化为二甲苯 | |
JPH11501286A (ja) | ゼオライト結合ゼオライト触媒を用いる炭化水素転化プロセス | |
CN1934228A (zh) | 烷基芳烃的选择催化加氢脱烷基化的方法 | |
CN1906272A (zh) | 烷基芳族烃的催化加氢脱烷基化方法 | |
CN1356927A (zh) | 多孔无机氧化物的含金属的宏观结构,其制备方法和用途 | |
CN101722035A (zh) | 具有形状择形功能的催化剂 | |
CN101081370A (zh) | Zsm-5/sapo-11复合沸石和催化裂化汽油加氢改质催化剂及其制备方法 | |
CN103638967B (zh) | 含有nes结构类型沸石和euo结构类型沸石的催化剂,及其用途 | |
CN1164524A (zh) | 在两种沸石催化剂存在下烷基芳烃歧化和烷基转移的方法 | |
EP3386633B1 (en) | Catalyst composition and isomerisation process | |
CN114425404B (zh) | 增产二甲苯的催化剂和方法 | |
US7402545B2 (en) | Catalyst that comprises at least one bog-structured zeolite and its use in transalkylation of alkyl-aromatic hydrocarbons | |
Guillon et al. | d) Patent Application Publication tio, Pub. No: US 2005/0234279A1 | |
CN1253858A (zh) | 甲苯歧化与烷基转移的催化剂及工艺 | |
CN1162502A (zh) | 含有针沸石结构类型沸石的催化剂及其在烷基芳烃歧化作用和/或烷基转移作用中的应用 | |
CN104549474A (zh) | 无粘结剂纳米ZSM-5/β共生沸石分子筛催化剂及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110727 Termination date: 20200414 |
|
CF01 | Termination of patent right due to non-payment of annual fee |